Organic reactants for atomic layer deposition

ABSTRACT

A method for selectively depositing a metal oxide film is disclosed. In particular, the method comprises pulsing a metal or semi-metal precursor onto the substrate and pulsing an organic reactant onto the substrate. A reaction between the metal or semi-metal precursor and the organic reactant selectively forms a metal oxide film on either a dielectric layer or a metal layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation and claims priority to U.S. patent application Ser. No. 15/205,827 filed Jul. 8, 2016 titled ORGANIC REACTANTS FOR ATOMIC LAYER DEPOSITION, the disclosure of which is hereby incorporated by reference in its entirety.

FIELD OF INVENTION

The present disclosure generally relates to processes for manufacturing electronic devices. More particularly, the disclosure relates to selectively forming films through cyclic processes such as ALD or sequential/cyclic CVD. Specifically, the disclosure discloses methods to selectively form ALD or sequential/cyclic CVD films with organic reactants.

BACKGROUND OF THE DISCLOSURE

Water (H₂O) has been often used for forming oxides in atomic layer deposition (ALD) processes. Water is a polar molecule due to its lone electron pair. Water is also reactive with many metal halides, which makes it a candidate for some ALD oxide processes. When used as a reactant at low temperatures, however, water has displayed some undesirable behavior.

Most notably, the presence of water as a reactant increases the time to sufficiently purge the tool during an ALD deposition cycle. Specifically, at low temperatures, water tends to stick to various surfaces, including substrates and tools with hydrophilic materials. The sticking of water may make it difficult to purge water from the system and it may cause loss of selectivity if water-based processes are applied on selective deposition schemes. In addition, the nature of water may oxidize some of the surfaces present on the substrate, which in some instances is not desirable.

Prior approaches have described using carboxylic acids for ALD of some metal oxides. However, these have not enabled selective deposition.

As a result, a method for ALD formation of a film that displays efficient purging and effective modification of the surface is desired.

SUMMARY OF THE DISCLOSURE

In accordance with at least one embodiment of the invention, a method of selectively forming a metal oxide is disclosed. The method comprises: providing a substrate comprising a dielectric layer and a layer comprising metal for processing in a reaction chamber; exposing the substrate to a metal or semi-metal precursor; exposing the substrate to a purging gas and/or a vacuum; exposing the substrate to an organic reactant; and exposing the substrate to a purging gas and/or the vacuum; wherein a reaction between the metal or semi-metal precursor and the organic reactant selectively forms a metal oxide layer on either the dielectric layer or layer comprising metal. In some embodiments the method of selectively forming a metal oxide comprises a cyclic process using a metal or semi-metal precursor and an organic reactant. In some embodiments the method of selectively forming a metal oxide using a metal or semi-metal precursor and an organic reactant comprises an ALD process. In some embodiments the method of selectively forming a metal oxide process using a metal or semi-metal precursor and an organic reactant comprises a cyclic or sequential CVD process using a metal or semi-metal precursor and an organic reactant. In some embodiments utilizing the cyclic or sequential CVD process, the metal or semi-metal precursor is partly decomposing on the surface. In some embodiments utilizing the cyclic or sequential CVD process, gas-phase reactions of the metal or semi-metal precursor and the organic reactant are substantially avoided. In accordance with exemplary aspects of these embodiments, the selective formation of the metal oxide layer occurs with use of an etchant before and/or after the formation of the metal oxide layer.

For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention have been described herein above. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught or suggested herein without necessarily achieving other objects or advantages as may be taught or suggested herein.

All of these embodiments are intended to be within the scope of the invention herein disclosed. These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments having reference to the attached figures, the invention not being limited to any particular embodiment(s) disclosed.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

These and other features, aspects, and advantages of the invention disclosed herein are described below with reference to the drawings of certain embodiments, which are intended to illustrate and not to limit the invention.

FIG. 1 is a cross-sectional view of a semiconductor device in accordance with at least one embodiment of the invention.

FIG. 2 is a cross-sectional view of a semiconductor device in accordance with at least one embodiment of the invention.

FIG. 3 is a cross-sectional view of a semiconductor device in accordance with at least one embodiment of the invention.

FIG. 4 is a flow chart of a method in accordance with at least one embodiment of the invention.

FIG. 5 is a flow chart of a method in accordance with at least one embodiment of the invention.

It will be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of illustrated embodiments of the present disclosure.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Although certain embodiments and examples are disclosed below, it will be understood by those in the art that the invention extends beyond the specifically disclosed embodiments and/or uses of the invention and obvious modifications and equivalents thereof. Thus, it is intended that the scope of the invention disclosed should not be limited by the particular disclosed embodiments described below.

For selective deposition processes, efficient purging is desirable. Efficient purging may allow for selectivity to take place, as the chemical vapor deposition (CVD) type of gas phase reactions are significantly reduced or absent. Additionally, it is generally desirable for selectivity to have surfaces present with only desired reactivity towards the deposition chemistry. For example, for some surfaces no reaction with the precursors (or reactants) is desired, and for other surfaces quick and complete reactions with the precursors (or reactants) are desired. If not present naturally, surfaces may be modified to exhibit the desired reactivity. For example, some surfaces can be treated to slow down the rate or completely inhibit a certain type of reaction. Surface modifications may be employed when using precursors (or reactants) with undesired reactivity towards a surface present in the system.

When using water as a reactant, the above goal of efficient purging is difficult to achieve. Water molecules are said to be polar because they exhibit an external dipole moment. This causes water to stick easily on surfaces. If water is used in selective deposition schemes, surface modifications may be used to passivate the surfaces against water. One example of such a passivation may include fluorinated or highly methyl covered surfaces, exhibiting high water contact angle. Water contact angle is a measure of the surface energy towards water. Surfaces with high water contact angle are typically passive against water. Additionally, the nature of water makes achieving only the right kind of surface reactivity more difficult, possibly resulting in a desire for surface modifications to protect a formed material, for example. Especially at temperature ranges of 100-150° C., water may prove to be problematic to remove at time scales suitable for production, due to the extended periods of time used to fully purge the water from the system and all the surfaces. Such temperatures may be encountered in many parts of a film deposition tool, outside the film deposition region.

Organic reactants, such as formic acid (HCOOH) or other carboxylic acids, may prove to be a better choice for ALD processes due to their properties. Specifically, organic reactants are not generally polar substances that stick to surfaces. In addition, organic reactants have a different nature when compared to water. Specifically, HCOOH may be able to produce reductive reactions. Additionally, organic reactants such as HCOOH begin decomposing at elevated temperatures and do not liberate H₂O at 100-150° C.

In some embodiments, the organic reactant is a vapor phase organic reactant that may demonstrate thermal stability within a range of process temperatures. For example, the vapor phase organic reactant may be thermally stable across a desired range of process temperatures such that growth-disturbing condensable phases do not form on the substrate and/or the vapor phase organic reactant does not generate harmful levels of impurities on the substrate surface through thermal decomposition. In some embodiments, the vapor phase organic reactant may exhibit sufficient vapor pressure such that a desired quantity of chemical molecules is present in the gas phase near the substrate surface to enable the reduction reactions.

In some embodiments, a vapor phase organic reactant may be selected based on its ability to decompose into two or more reactive components, at least one of which can react with the surface.

In some embodiments, the vapor phase organic reactant may comprise formic acid. In some embodiments, the vapor phase organic reactant may comprise acetic acid (CH₃COOH) and/or propanoic acid (CH₃CH₂COOH). In some embodiments, the (e.g., vapor phase) organic reactant may include an alcohol. In some embodiments, the (e.g., vapor phase) organic reactant may include an aldehyde. In some embodiments, the (e.g., vapor phase) organic reactant may have at least one functional group selected from the group consisting of alcohol (—OH), aldehyde (—CHO), and carboxylic acid (—COOH).

Without being limited by any particular theory or mode of operation, the process for depositing metal oxide films selectively using organic reactants may also reduce the metal or metal oxide surfaces present on the substrate. For example, the carboxylic acid may reduce oxidized copper such that the oxidized copper may be restored to its elemental state. In some embodiments, the organic reactant, when used as oxygen source, may keep the metal surface as elemental metal or metallic or conductive state.

Organic reactants containing at least one alcohol group may be preferably selected from the group consisting of primary alcohols, secondary alcohols, tertiary alcohols, polyhydroxy alcohols, cyclic alcohols, aromatic alcohols, and other derivatives of alcohols.

Preferred primary alcohols have an -OH group attached to a carbon atom, which may be bonded to another carbon atom, in particular primary alcohols, according to the general formula (I): R¹—OH   (I) wherein R¹ is a linear or branched C₁-C₂₀ alkyl or alkenyl groups, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl groups. Examples of preferred primary alcohols include methanol, ethanol, propanol, butanol, 2-methyl propanol and 2-methyl butanol.

Preferred secondary alcohols have an —OH group attached to a carbon atom that is bonded to two other carbon atoms. In particular, preferred secondary alcohols have the general formula (II):

wherein each R¹ is selected independently from the group of linear or branched C₁-C₂₀ alkyl and alkenyl groups, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl groups. Examples of preferred secondary alcohols include 2-propanol and 2-butanol.

Preferred tertiary alcohols have an —OH group attached to a carbon atom that is bonded to three other carbon atoms. In particular, preferred tertiary alcohols have the general formula (III):

wherein each R¹ is selected independently from the group of linear or branched C₁-C₂₀ alkyl and alkenyl groups, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl groups. An example of a preferred tertiary alcohol is tert-butanol.

Preferred polyhydroxy alcohols, such as diols and triols, have primary, secondary and/or tertiary alcohol groups as described above. Examples of preferred polyhydroxy alcohol are ethylene glycol and glycerol.

Preferred cyclic alcohols have an —OH group attached to at least one carbon atom which is part of a ring of 1 to 10, more preferably 5-6 carbon atoms.

Preferred aromatic alcohols have at least one —OH group attached either to a benzene ring or to a carbon atom in a side chain.

Preferred reactants containing at least one aldehyde group (—CHO) are selected from the group consisting of compounds having the general formula (V), alkanedial compounds having the general formula (VI), and other derivatives of aldehydes.

Thus, in one embodiment preferred reactants are aldehydes having the general formula (V): R³—CHO   (V) wherein R³ is selected from the group consisting of hydrogen and linear or branched C₁-C₂₀ alkyl and alkenyl groups, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl groups. More preferably, R³ is selected from the group consisting of methyl or ethyl groups. Examples of preferred compounds according to formula (V) are formaldehyde, acetaldehyde and butyraldehyde.

In another embodiment preferred reactants are aldehydes having the general formula (VI): OHC—R⁴—CHO   (VI) wherein R⁴ is a linear or branched C₁-C₂₀ saturated or unsaturated hydrocarbon. Alternatively, the aldehyde groups may be directly bonded to each other (R⁴ is null).

Organic reactants containing at least one —COOH group are preferably selected from the group consisting of compounds of the general formula (VII), polycarboxylic acids, and other derivatives of carboxylic acids.

Thus, in one embodiment, preferred organic reactants may be carboxylic acids having the general formula (VII): R⁵—COOH   (VII) wherein R⁵ is hydrogen or linear or branched C₁-C₂₀ alkyl or alkenyl group, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl, more preferably methyl or ethyl groups. In some embodiments, R⁵ is a linear or branched C₁-C₃ alkyl or alkenyl group. Examples of preferred compounds according to formula (VII) are formic acid, propanoic acid and acetic acid, most preferably formic acid (HCOOH).

In some embodiments, the organic reactant demonstrates desired vapor pressure such that the organic reactant may be volatized without heating the organic reactant. In some embodiments, such an organic reactant may comprise only one carboxyl group (—COOH).

In some embodiments, the organic reactant may be heated to volatize the organic reactant prior to delivering the volatized organic reactant to the substrate surface. In some embodiments, such an organic reactant may comprise a dicarboxylic acid, including an oxalic acid.

In some embodiments, the organic reactant may comprise less than about 15 weight % water (H₂O). In some embodiments, the organic reactant may comprise less than about 5 weight % water, less than about 2 weight % or less than about 1 weight %. For example, the organic reactant may comprise less than about 0.5, less than about 0.1, or less than about 0.05 weight % water. In some embodiments, the organic reactant may not comprise metal. In some embodiments, the organic reactant may comprise only carbon, hydrogen, and oxygen.

As described herein, an organic reactant may decompose into two or more reactive components during the deposition. For example, some of the carboxylic acid delivered to a reaction space may decompose into carbon monoxide (CO) and hydrogen gas (H₂) during the deposition process, such that one or more of the carbon monoxide (CO) and hydrogen gas (H₂) may help keep metal or metallic surfaces in its original state, i.e., prevent oxidation of the metal or metallic surfaces, or reduce them to elemental or metallic state. In this way, a substrate surface may be exposed to hydrogen gas (H₂) even though no hydrogen gas (H₂) is actively provided into the reaction space from an external source.

In some embodiments, the organic reactant may be stored in a liquid phase and subsequently volatized prior to being delivered to the substrate surface. In some embodiments, the organic reactant may be in vapor phase in the reaction space, such that the reaction space is substantially free of any liquid phase reactants. For example, the organic reactant may be in liquid phase during storage and may be subsequently volatized prior to delivery into a reaction chamber, such that only or substantially only organic reactant in the vapor phase is present within the reaction chamber.

In some embodiments, an organic reactant may be stored in a gas bubbler and can be supplied to the reaction chamber from the gas bubbler. In some embodiments, the organic reactant may be stored in a gas bubbler at around room temperature (e.g., from about 20° C. to about 25° C.). For example, the organic reactant gas may be pulsed into the reaction chamber from the gas bubbler during a cycle of the deposition process. In some embodiments, a mass flow rate of the organic reactant may be controlled by controlling the extent to which a valve for delivering the organic reactant into the reactor chamber is kept open (e.g., a needle valve). For example, a mass flow rate may be selected such that a quantity of the organic reactant may be flowed into the reaction chamber during a cycle of the deposition process to facilitate metal surface reduction or protecting the metal surface from being oxidized or facilitate increased selectivity.

Embodiments of the invention may be directed to selectively deposit metal or semi-metal oxide film using an organic reactant source on micrometer-scale (or smaller) features during integrated circuit fabrication. For example, process flows described herein may be used to manufacture features having a size less than 100 micrometers, less than 1 micrometer, or less than 200 nm. In the case of selective deposition of tungsten on copper for interconnects, the size of the feature or line width may be less than 1 micrometer, less than 200 nm, less than 100 nm, or less than 50 nm. One of ordinary skill in the art may recognize that selective deposition on larger features and in other contexts is possible using the disclosed methods.

As mentioned above, the selectivity may be expressed as the ratio of material formed on the first surface (A) minus the amount of material formed on the second surface (B) to amount of material formed on the first surface (A) (i.e., selectivity can be given as a percentage calculated by [(deposition on first surface)−(deposition on second surface)]/(deposition on the first surface) or [(A−B)/A]). Preferably, the selectivity is above about 70%, above about 80%, more preferably above 90%, even more preferably above 95%, or most preferably about 100%. In some cases, selectivity above 80% may be acceptable for certain applications. In some cases, selectivity above 50% may be acceptable for certain applications. In some embodiments, the deposition temperature may be selected such that the selectivity is above about 90%. In some embodiments, the deposition temperature may be selected such that a selectivity of about 100% is achieved.

In some embodiments, the thickness of the film that is selectively deposited may be less than about 100 nm, less than about 50 nm, about 25 nm or less than about 10 nm, in some embodiments, from about 0.5 nm to about 100 nm or from about 1 nm to about 50 nm. However, in some cases a desired level of selectivity, for example more than 50%, more preferably more than 80%, is achieved with the thicknesses of the selectively deposited film being over about 2.5 nm , about 5 nm, over about 10 nm, over about 25 nm or over about 50 nm.

FIG. 1 illustrates a semiconductor device 100 in accordance with at least one embodiment of the invention. The semiconductor device 100 may comprise a substrate 110, a metal layer 120, and a dielectric layer 130. The substrate 110 may comprise a material such as silicon or silicon germanium. The metal layer 120 may comprise a material such as tungsten, cobalt or copper. The dielectric layer 130 may comprise a material such as silicon dioxide, or various low-k dielectric layers.

The substrate may comprise various types of materials. When manufacturing integrated circuits, the substrate typically comprises a number of thin films with varying chemical and physical properties. For example and without limitation, the substrate may comprise a silicon-containing layer and a metal layer. In some embodiments, the substrate can comprise metal carbide. In some embodiments, the substrate can comprise a conductive oxide.

In at least one embodiment, the substrate may have a first surface comprising a metal, referred to herein as the first metal surface or first metallic surface. The first surface may be essentially an elemental metal, such as Cu or Co. In other embodiments, the first surface may comprise a metal nitride or a transition metal. The transition metal may be selected from the group: Ti, V, Cr, Mn, Nb, Mo, Ru, Rh, Pd, Ag, Au, Hf, Ta, W, Re, Os, Ir, and Pt. In some embodiments, the first surface may comprise a noble metal, such as Au, Pt, Ir, Pd, Os, Ag, Re, Rh, and Ru, for example. In other embodiments, the metal or semi-metal film deposited using one or more organic reactants as oxygen source may be selectively deposited on a metal oxide surface relative to other surfaces, where the metal oxide surface may be, for example a WO_(x), HfO_(x), TiO_(x), AlO_(x), or ZrO_(x) surface. In some embodiments, a metal oxide surface may be an oxidized surface of a metallic material.

In at least one embodiment, the substrate may have a second surface which is preferably a silicon containing surface, referred to herein as the second silicon containing surface or second surface comprising silicon. In some embodiments, the silicon containing surface may comprise, for example, SiO₂ or surface comprising Si—O bonds. In some embodiments, the second surface may comprise silicon oxide, silicon nitride, silicon carbide, silicon oxynitride, silicon dioxide, or mixtures thereof. In some embodiments, the material comprising the second surface may be a porous material. In some embodiments, the porous material may contain pores which are connected to each other, while in other embodiments, the pores are not connected to each other. In some embodiments, the second surface may comprise a low-k material, defined as an insulator with a dielectric value below about 4.0. In some embodiments, the dielectric value of the low-k material may be below about 3.5, below about 3.0, below about 2.5, or below about 2.3.

FIG. 2 illustrates the semiconductor device 100 in accordance with at least one embodiment of the invention. The semiconductor device 100 includes a metal oxide 140 deposited on the dielectric layer 130. Metal oxides that may be formed include a germanium, transition metal oxide or metal oxide films, such as germanium oxide (GeO₂), titanium oxide (TiO₂), hafnium oxide (HfO₂), or zirconium oxide (ZrO₂), for example. In some embodiments the metal oxide film is not silicon dioxide film and/or in some embodiments the metal oxide film does not comprise silicon. For simplicity reasons germanium here in is considered to be a metal. In some embodiments the germanium oxide layer comprises Ge—O bonds and does not comprise substantial amounts of metals.

FIG. 3 illustrates the semiconductor device 100 in accordance with at least one embodiment of the invention. The semiconductor device 100 includes a metal oxide 140 deposited on the metal layer 120. Metal oxides that may be formed include a germanium oxide (GeO₂), titanium oxide (TiO₂), hafnium oxide (HfO₂), or zirconium oxide (ZrO₂), for example.

Many of the metal oxides that are listed above may be deposited using water as a precursor, but processes in accordance with the present invention may avoid the issues associated using water as a precursor. FIG. 4 illustrates an ALD method in accordance with at least one embodiment of the invention. The ALD method 200 may deposit a metal oxide film on either the dielectric layer or the metal layer. It should be noted that although referred to an ALD method, such methods as described herein can be a cyclic or sequential CVD process, such as a CVD process in which gas-phase reactions are avoided.

The ALD method 200 includes a step of pulsing a metal or semi-metal precursor 210. Metal or semi-metal precursors that may be used in step 210 may include germanium alkylamide, such as germanium dialkylamine, like (Ge(NMe₂)₄). In some embodiments the metal or semi-metal precursor is a metal halide, such as transition metal halide or for example, aluminum halide, such as aluminum chloride. In some embodiments the metal or semi-metal precursor comprises halide, such as chlorine. In some embodiments the metal or semi-metal precursor is a metal chloride, such as transition metal chloride, such as TiCl₄, HfCl₄ or ZrCl₄. In some embodiments the metal or semi-metal precursor is a metalorganic precursor, such as metalorganic precursor comprising transition metal. In some embodiments the metal or semi-metal precursor is a metal alkylamine precursor, such as Ti(NEtMe)₄, Hf(NEtMe)₄, or Zr(NEtMe)₄. In some embodiments the metal or semi-metal precursor is organometallic precursor, such as alkylaluminum compounds, for example trimethylaluminum (TMA), or such as cyclopentadienyl compounds of Ti, Hf or Zr, for example, (pentamethylcyclopentadienyl)trimethoxytitanium (Me₅Cp)Ti(OMe)₃, bis(methylcyclopentadienyl)methoxymethylhafnium (MeCp)₂Hf(OMe)Me or tris(dimethylamino)cyclopentadienylzirconium CpZr(NMe₂)₃. The pulse step 210 may take place for a time duration ranging between 0.01 and 60 seconds, from about 0.1 to about 30 seconds or from about 0.2 to about 10 seconds at temperatures ranging between about 0 to about 750° C., from about 50 to about 500° C., or from about 150 and 350° C. Step 210 may then be followed by a purge step 220, which would remove any excess metal or semi-metal precursors.

A number of different Ge precursors can be used in the deposition processes. In some embodiments the Ge precursor is tetravalent (i.e. Ge has an oxidation state of +IV). In some embodiments, the Ge precursor is not divalent (i.e., Ge has an oxidation state of +II). In some embodiments, the Ge precursor may comprise at least one alkoxide ligand. In some embodiments, the Ge precursor may comprise at least one amine or alkylamine ligand. In some embodiments the Ge precursor is a metal-organic or organometallic compound. In some embodiments the Ge precursor comprises at least one halide ligand. In some embodiments the Ge precursor does not comprise a halide ligand.

For example, Ge precursors from formulas VIII-X below may be used in some embodiments: Ge(NR^(I)R^(II))₄   (VIII) wherein R^(I) can be independently selected from the group consisting of hydrogen, alkyl and substituted alkyl; and R^(II) can be independently selected from the group consisting of alkyl and substituted alkyl; Ge(NR^(I)R^(II))₄   (IX) wherein the x is an integer from 1 to 4; R^(I) can be independently selected from the group consisting of hydrogen, alkyl and substituted alkyl; and R^(II) can be independently selected from the group consisting of alkyl and substituted alkyl; A can be independently selected from the group consisting of alkyl, alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines, halide, and hydrogen; Ge_(n)(NR^(I)R^(II))_(2n+2)   (X) wherein the n is an integer from 1 to 3; R^(I) can be independently selected from the group consisting of hydrogen, alkyl and substituted alkyl; and R^(II) can be independently selected from the group consisting of alkyl and substituted alkyl.

The ALD method 200 may also include a step of pulsing an organic reactant 230. Organic reactant may include formic acid (HCOOH), any simple carboxylic acid, or any precursor that might decompose into CO, CO₂, or any other by-product species, and H₂O, or any other organic precursor noted herein. For example, a step 230 pulsing formic acid (and/or another organic reactant) may use a purity of organic reactant, such as formic acid and/or other organic reactant of at least 90%, more preferably at least 95%, and more preferably at least 98%, in order to obtain a properly deposited layer. The pulse step 230 may take place for a time duration ranging between 0.01 and 60 seconds, from about 0.1 to about 30 seconds or from about 0.2 to about 10 seconds at a temperature range ranging between about 0 to about 750° C., from about 50 to about 500 C or from about 150 and 350° C. Step 230 may then be followed by a purge step 240, which would remove any excess organic reactant(s). The steps of the ALD method 200 may be repeated to form an oxide layer of a desired thickness. In some embodiments, the purge step of the organic reactant(s) may be less than about 10 seconds, less than about 5 seconds, less than about 2 seconds, less than about 1 second, less than about 0.5 seconds while still retaining selective deposition. In some embodiments, the same degree of selectivity may not be retained if a water or other oxygen source than an organic reactant is used. While the exemplary pulse and purge times mentioned above may be applicable to many different types of reactors, single wafer, or mini-batch reactors, pulse and purge times may be higher in case of batch reactors with high surface areas. Any of the purge steps as discussed herein can use an inert gas, such nitrogen and/or a noble gas, such as argon and/or helium.

The ALD method 200 enables selective deposition on a substrate comprising at least two different surfaces, for example, a first surface comprising metal, such as Cu, and second surface comprising silicon, such as silicon dioxide or low-k material. As a result, for example, a metal oxide film can be formed on the dielectric material, while the metal surface can remain uncovered or vice versa. In addition, there may be more efficient purging of the carboxylic acid or other organic reactant due to its lower polarity in comparison to water. The use of ozone (O₃) or oxygen plasma or oxygen atoms or oxygen radicals may be avoided due to its tendency to oxidize metals or metallic materials or surfaces easily as well as destroying the selectivity. In some embodiments, plasma may not be used in the deposition process. Although described in connection with ALD processing, method 200 can similarly be performed using sequential/cyclic CVD.

In some embodiments, the selective deposited film using organic reactant may have a growth rate of less than about 5 Å/cycle, less than about 2.5 Å/cycle, less than about 1.5 Å/cycle or less than about 1.0 Å/cycle. In other embodiments the selective deposited film using organic reactant has a growth rate from about 0.01 to about 5 Å/cycle, from about 0.05 to about 2.5 Å/cycle or from about 0.1 to about 2 Å/cycle.

FIG. 5 illustrates an ALD (or sequential/cyclic CVD) method in accordance with at least one embodiment of the invention. The ALD method 300 may deposit a metal oxide film on either a dielectric layer or a metal layer.

The ALD method 300 may include a step of pulsing an organic reactant 310. Organic reactants may include formic acid (HCOOH), any simple carboxylic acid, or any precursor that might decompose into CO, CO₂, or any other by-product species and H₂O, or other organic reactant as described herein. For example, a step 310 pulsing formic acid or other organic reactant may use a purity of formic acid or other organic reactant of at least 90%, at least 95%, and more preferably at least 98% in order to obtain a properly deposited layer. The pulse step 310 may take place for a time duration ranging between 0.01 and 60 seconds, from about 0.1 to about 30 seconds, or from about 0.2 to about 10 seconds at temperatures ranging between 0 and 750° C., between 50 and 500° C., or between 150 and 350° C. Step 310 may then be followed by a purge step 320, which would remove any excess organic reactants.

The steps of the ALD method 300 may be repeated to form an oxide layer of a desired thickness. In some embodiments, the purge step of the organic reactant may be less than about 10 seconds, less than about 5 seconds, less than about 2 seconds, less than about 1 second, less than about 0.5 seconds while still retaining selective deposition. In some embodiments, the same degree of selectivity may not be retained if a water or other oxygen source than the organic reactant is used. While the exemplary pulse and purge times mentioned above may be applicable to many different types of reactors, single wafer, or mini-batch reactors, pulse and purge times may be higher in case of batch reactors with high surface areas.

The ALD method 300 includes a step of pulsing a metal or semi-metal precursor 330. Metal or semi-metal precursors that may be used in step 330 may include germanium alkylamide, such as germanium dialkylamine like (Ge(NMe₂)₄), for example. The pulse step 330 may take place for a time duration ranging between 0.01 and 60 seconds, from about 0.1 to about 30 seconds, or from about 0.2 to about 10 seconds at temperatures ranging between about 0 to about 750° C., from about 50 to about 500° C., or from about 150 and 350° C. Step 330 may then be followed by a purge step 340, which would remove any excess metal or semi-metal precursors. The steps of the ALD method 300 may be repeated to form an oxide layer of a desired thickness.

The ALD method 300 enables selective deposition on a substrate comprising at least two different surfaces, for example, a first surface comprising metal, such as Cu, and second surface comprising silicon, such as silicon dioxide or low-k silicon. As a result, for example, a metal oxide film can be formed on the dielectric, while the metal surface can remain uncovered or vice versa. In addition, there may be more efficient purging of the carboxylic acid reactant due to its lower polarity in comparison to water. The use of ozone (O₃), oxygen plasma, oxygen atoms, or oxygen radicals may be avoided due to its tendency to oxidize metals or metallic materials or surfaces easily as well as destroying the selectivity. In some embodiments, plasma may not be used in the deposition process.

The ALD method 300 may modify the metal surface of the substrate. For example, the carboxylic acid (or other organic reactant) may reduce a metallic surface or elemental metal, such as copper oxide (CuO), surface to metallic or elemental metal, such as elemental copper. In addition, the carboxylic acid may remove any remaining passivation layer on the metal surface, such as benzotriazole (BTA). Both of these effects are benefits because removal of the passivation layer or reduction to straight copper may both be capable of enabling selective growth. Similar to method 200, method 300 may be a cyclic CVC process, rather than an ALD process.

Quality of the metal oxide layer deposited through either ALD method 200 or ALD method 300 may be judged by a selectivity of a surface of the metal oxide layer. For example, the selectivity may be quantified by a thickness of the metal oxide layer in relation to thickness deposited on the desired layer.

The particular implementations shown and described are illustrative of the invention and its best mode and are not intended to otherwise limit the scope of the aspects and implementations in any way. Indeed, for the sake of brevity, conventional manufacturing, connection, preparation, and other functional aspects of the system may not be described in detail. Furthermore, the connecting lines shown in the various figures are intended to represent exemplary functional relationships and/or physical couplings between the various elements. Many alternative or additional functional relationship or physical connections may be present in the practical system, and/or may be absent in some embodiments.

It is to be understood that the configurations and/or approaches described herein are exemplary in nature, and that these specific embodiments or examples are not to be considered in a limiting sense, because numerous variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Thus, the various acts illustrated may be performed in the sequence illustrated, in other sequences, or omitted in some cases.

The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various processes, systems, and configurations, and other features, functions, acts, and/or properties disclosed herein, as well as any and all equivalents thereof. 

We claim:
 1. A method of selectively forming a metal oxide comprising: providing a substrate comprising a dielectric layer and a layer comprising metal nitride, the metal nitride layer having passivation thereon, for processing in a reaction chamber; exposing the substrate to a metal or semi-metal precursor comprising at least one halide ligand; exposing the substrate to one or more of a first purging step and a vacuum; exposing the substrate to an organic reactant comprising formic acid; and exposing the substrate to one or more of a second purging step and the vacuum; wherein the formic acid decomposes to produce H₂O; wherein exposing the substrate to the organic reactant comprises removing the passivation from the layer comprising metal nitride, the passivation comprising benzotriazole; wherein a reaction between the metal or semi-metal precursor and the organic reactant selectively forms a metal oxide on the dielectric layer, and wherein a selectivity of formation of the metal oxide layer on the dielectric layer, as defined as a ratio of a first amount formed on the dielectric layer minus a second amount formed on the layer comprising metal nitride to the first amount, is greater than 50%.
 2. The method of claim 1, wherein the organic reactant comprises water in an amount up to 15 weight %.
 3. The method of claim 2, wherein the organic reactant comprises less than about 5 weight % water.
 4. The method of claim 1, wherein the metal or semi-metal precursor comprises germanium.
 5. The method of claim 1, wherein the organic reactant decomposes to produce CO.
 6. The method of claim 1, wherein the organic reactant decomposes into two or more reactive components comprising water and CO.
 7. The method of claim 1, wherein the organic reactant is stored in a liquid phase.
 8. The method of claim 1, wherein the organic reactant is stored in a gas bubbler.
 9. The method of claim 1, wherein the metal oxide layer comprises one or more of titanium oxide and tungsten oxide.
 10. The method of claim 1, wherein exposing the substrate to the organic reactant comprises decomposing the organic reactant to carbon monoxide and hydrogen gas.
 11. The method of claim 10, wherein the method does not include directly supplying hydrogen gas to reaction chamber.
 12. A method of selectively forming a metal oxide comprising: providing a substrate comprising a dielectric layer and a layer comprising metal nitride for processing in a reaction chamber; exposing the substrate to a metal or semi-metal precursor comprising at least one halide ligand; exposing the substrate to one or more of a first purging step and a vacuum; exposing the substrate to an organic reactant comprising formic acid and water; and exposing the substrate to one or more of a second purging step and the vacuum; wherein a reaction between the metal or semi-metal precursor and the organic reactant selectively forms a metal oxide layer on the dielectric layer, wherein a selectivity of formation of the metal oxide layer on the dielectric layer, as defined as a ratio of a first amount formed on the dielectric layer minus a second amount formed on the layer comprising metal nitride to the first amount, is greater than 50%, wherein exposing the substrate to the organic reactant comprises removing passivation comprising benzotriazole from the layer comprising metal nitride, and wherein the metal or semi-metal precursor comprises one or more of tungsten and titanium.
 13. The method of claim 12, wherein the layer comprising metal nitride consists essentially of metal nitride.
 14. The method of claim 12, wherein the organic reactant comprises water in an amount up to 15 weight %.
 15. The method of claim 12, wherein the organic reactant comprises water in an amount up to 5 weight %. 